CN101792529B - Composition for a silicone resin - Google Patents
Composition for a silicone resin Download PDFInfo
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- CN101792529B CN101792529B CN2009102619227A CN200910261922A CN101792529B CN 101792529 B CN101792529 B CN 101792529B CN 2009102619227 A CN2009102619227 A CN 2009102619227A CN 200910261922 A CN200910261922 A CN 200910261922A CN 101792529 B CN101792529 B CN 101792529B
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- silicone resin
- metal oxide
- methyl silsesquioxane
- microparticle
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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Abstract
A composition for a silicone resin containing a poly(methyl silsesquioxane) derivative having an alkoxysilyl group at an end of a molecule, and fine metal oxide particles having a reactive functional group on the surface thereof, wherein the composition further contains at least one compound selected from the group consisting of disilanol derivatives having silanol groups at both ends of a molecule and a monofunctional silane derivative represented by the formula (II): wherein X is an alkoxy group or a halogen atom. The silicone resin composition of the present invention can be suitably used as, for example, materials for encapsulating photosemiconductor elements for use in backlights for liquid crystal displays, traffic lights, outdoor big displays, advertisement sign boards, and the like.
Description
Technical field
The present invention relates to a kind of silicone resin composition.More specifically, relate to that the transparency is excellent, composition, transparency excellence, the high-adhesion silicone resin for high strength and flexibility and the silicone resin composition with stretching slip resistance and excellent heat resistance.In addition, relate to silicon resin composition that said composition reaction is obtained and the molding of manufacture method and said composition thereof.
Background technology
In recent years, the thermotolerance of silicone resin, weather resistance, weather variability excellence, therefore the use in the environment of environment for use harshness increases.Particularly silicone resin without absorption, so the transparency is excellent, thereby is suitable for needing the purposes of the transparency and environment for use harshness in visible region.
For example, a little less than the common intermolecular forces of polydimethyl silyl type siloxane, even be the high molecular body, also as viscous liquid, exist.Therefore, as the method for the intensity that improves polydimethyl silyl silicone derivative, the 3 functionality T unit or the 4 functionality Q unit that usually adopt importing can in molecule, form crosslinked configuration improve the method (referring to JP 2001-200162 communique) that degree of crosslinking is gained in strength.Also the known degree of crystallinity that improves resin by importing substituting group that the phenyl equal-volume is large makes the method (referring to JP 2000-265150 communique) of resin hardens.
Show in the 2005-513195 communique the spy, disclose in silicone resin and to have added filler and put forward high-intensity technology thering is flexibility simultaneously.
In addition, silicone based pressure sensitive adhesives demonstrates good wet fastness or electrical insulating property, so be widely used in electronic unit.Along with miniaturization, the high capacity of e-machine in recent years, it is complicated that its manufacturing process becomes, so require further to improve the quality of silicone based pressure sensitive adhesives.
In the past, as silicone based binding agent, used the silicon composition of adhesive addition-crosslinked property or silicone elastomer derivative by it etc. by the person.But, the organosilyl cohesiveness derivative by pure siloxane is insufficient, therefore usually adopts functional groups such as importing epoxy group(ing), amino, sulfydryl to carry out the method (referring to JP 2001-200162 communique) of the prime treatment of the organically-modified method of resin or the filler that use has this functional group.
In JP 2000-265150 communique, disclose by adding silicon oxide particle that specific surface area is little to there is the silicon composition of low-thermal-expansion rate and high adhesion.Improve cohesiveness by processing aids such as use softening agent in special table 2005-513195 communique.
In addition, as improve stable on heating binding agent, disclose do not carry out above-mentioned organically-modified, by derivative organosilicon binding agents (referring to the spy, showing the 2004-502021 communique) such as organopolysiloxane untreated rubber and bridging property polyalkoxysilanes.
Summary of the invention
The present invention relates to
(1) a kind of silicone resin composition, be to contain in molecular end there is the poly methyl silsesquioxane derivative of alkoxysilyl and there is at microparticle surfaces the silicone resin composition that the metal oxide microparticle of reactive functional groups forms, also contain at least a kind in the 1 functional silanes derivative that two ends that are selected from molecule have the disilane alcohol derivate of silanol group and formula (II) expression:
[changing 1]
(in formula, X means alkoxyl group or halogen atom);
(2) a kind of silicon resin composition, make after microparticle surfaces has the metal oxide microparticle of reactive functional groups and has the poly methyl silsesquioxane derivative polymerization reaction take place of alkoxysilyl in molecular end, make the polymkeric substance that obtains further and be selected from two ends at molecule and there is at least 1 speciogenesis polyreaction in the disilane alcohol derivate of silanol group and 1 functional silanes derivative that formula (I I) means and obtain
[changing 2]
(in formula, X means alkoxyl group or halogen atom)
(3) manufacture method of the silicon resin composition of above-mentioned (2) comprises following operation: in molecular end, have the poly methyl silsesquioxane derivative of alkoxysilyl and have the operation of the metal oxide microparticle polymerization reaction take place of reactive functional groups at microparticle surfaces; And make the polymkeric substance that obtains in this operation and the operation that is selected from two ends at molecule and has at least 1 speciogenesis polyreaction in the disilane alcohol derivate of silanol group and 1 functional silanes derivative that formula (II) means;
[changing 3]
(in formula, X means alkoxyl group or halogen atom); And
(4) a kind of silicone resin molding, make the silicon resin composition of above-mentioned (2) be shaped and form.
The present invention relates to the transparency excellent and, molding with composition silicone resin for of high strength and flexibility, the silicon resin composition that said composition is reacted obtain and manufacture method thereof, said composition.In addition, the present invention relates to that the transparency is excellent, high-adhesion and there is the stretching slip resistance and, the molding of composition silicone resin for of excellent heat resistance, the silicon resin composition that said composition is reacted obtain and manufacture method thereof, said composition.
Silicone resin of the present invention with composition performance can provide the transparency excellent and, there is the excellent effect of the silicon resin composition of high strength and flexibility.In addition, silicone resin of the present invention with composition performance can provide that the transparency is excellent, high-adhesion and there is the stretching slip resistance and, the effect of the silicon resin composition of excellent heat resistance.
Above-mentioned and other advantage of the present invention is clear and definite by following explanation.
From the viewpoint of mechanical strength of resin, consider, even press the method modulation silicone resin of JP 2001-200162 communique, although be high strength but become fragile, in addition, even press the substituting group that JP 2000-265150 communique imports the large volume such as phenyl, although the degree of crystallinity of resin improves, the intensity raising as resin integral body, become fragile.Therefore, aforesaid method has coating agent etc. with advantages such as film protection surfaces, exists and is difficult to use in the thick film purposes or needs the purposes of bendability or need the problem of the purposes of flexibility.
In addition, as the spy shows the method for interpolation filler as described in the 2005-513195 communique, also be difficult to disperse filler, be difficult to obtain the material that the transparency is high.
On the other hand, from close-burning viewpoint, consider, although the cohesiveness excellence of the functional groups such as epoxy group(ing), amino and base material, thermotolerance is insufficient, if be exposed to for a long time under the high temperature more than 150 ℃, and cohesive force reduction, generation variable color etc.In addition, the silicon oxide particle added in the method for JP 2000-265150 communique is large, and dispersiveness is also insufficient, therefore obtains the poor material of the transparency.While according to the spy, showing 2005-513195 communique use processing aid, also can improve cohesiveness, but thermotolerance is insufficient, if be exposed to for a long time in high temperature, cohesive force reduces, and variable color etc. occurs.
In addition, although disclosed organosilicon binding agent excellent heat resistance in special table 2004-502021 communique, cohesive strength is still insufficient, requires further to improve.
Therefore, the inventor etc. have carried out research repeatedly in order to solve above-mentioned problem, found that and make thering is the metal oxide microparticle of reactive functional groups and being included in the reaction as the part of the alkoxysilyl in the poly methyl silsesquioxane derivative of silicone resin raw material at microparticle surfaces and carry out crosslinked as filler, can make this particulate disperse well, maintain the transparency, improve mechanical strength of resin simultaneously.And then, by using specific silane derivative as the silicone resin raw material, can keep the distinctive flexibility of organosilicon, in addition according to the kind of this silane derivative, without importing, organic functional group improves and the cohesiveness of base material, and thermotolerance also further improves, and has completed the present invention.
Silicone resin of the present invention contains in molecular end and has the poly methyl silsesquioxane derivative of alkoxysilyl and have the metal oxide microparticle of reactive functional groups at microparticle surfaces with composition, and then, as specific silane derivative, contain at least 1 that is selected from aftermentioned disilane alcohol derivate and 1 functional silanes derivative, can provide the silicon resin composition with various characteristics thus.Particularly, can enumerate following 2 modes.
Mode 1: a kind of silicone resin composition, be to contain in molecular end there is the poly methyl silsesquioxane derivative of alkoxysilyl and there is the silicone resin composition of the metal oxide microparticle of reactive functional groups at microparticle surfaces, and then contain the disilane alcohol derivate that there is silanol group at two ends of molecule;
Mode 2: a kind of silicone resin composition, be to contain in molecular end there is the poly methyl silsesquioxane derivative of alkoxysilyl and there is the silicone resin composition of the metal oxide microparticle of reactive functional groups at microparticle surfaces, and then contain the 1 functional silanes derivative that formula (II) means:
[changing 4]
(in formula, X means alkoxyl group or halogen atom)
It should be noted that, as resin composition of the present invention, also comprise as specific silane derivative contain simultaneously above-mentioned disilane alcohol derivate and 1 functional silanes derivative mode, be the mode of array mode 1 and mode 2.
The poly methyl silsesquioxane derivative is the condensation structure that cross-linking density is high, so be difficult to obtain the material of macromolecule.In the present invention, make to there is the poly methyl silsesquioxane derivative of reactive alkoxysilyl and there is the metal oxide microparticle polymerization reaction take place of reactive functional groups at microparticle surfaces in molecular end, the part of the part of the alkoxysilyl of poly methyl silsesquioxane derivative and the surface functional group of metal oxide microparticle occurs crosslinked by interactions such as covalent linkage or hydrogen bonds, disperse well thus this metal oxide microparticle, maintain the transparency, as the whole apparent upper polymer of resin, quantize simultaneously, so can there is physical strength, obdurability, wear resistance, the high strength of the excellents such as scratch resistance.
Therefore, in mode 1, after the crosslinking reaction of above-mentioned poly methyl silsesquioxane derivative and metal oxide microparticle, unreacted alkoxysilyl and there is the disilane alcohol derivate generation polycondensation of silanol group at two ends of molecule in this poly methyl silsesquioxane derivative, form thus the organosilicon unit that flexibility is high, thus can access the transparency excellent and, silicon resin composition with high strength and flexibility.
In addition, in mode 2, after the crosslinking reaction of above-mentioned poly methyl silsesquioxane derivative and metal oxide microparticle, the 1 functional silanes derivative block polymerization that in this poly methyl silsesquioxane derivative, unreacted alkoxysilyl through type (II) means,, the polymkeric substance and this 1 functionality organoalkoxysilane generation polycondensation that by crosslinking reaction, are obtained, can adjust cross-linkage of resin thus, thereby also can improve thermotolerance, can obtain the transparency excellent, have high strength and, the silicon resin composition of excellent heat resistance.In addition, the silicon resin composition obtained does not thus at room temperature have viscosity (tackiness), so the operability excellence shows viscosity by heating, and the performance high-adhesion.
The resinoid general name of organosilicon that poly methyl silsesquioxane derivative in mode 1 and 2 is oxygen atomicity is 1.5 with respect to the ratio of Siliciumatom number, as the poly methyl silsesquioxane derivative that there is alkoxysilyl in molecular end (following also referred to as the poly methyl silsesquioxane derivative), for example can enumerate and there is compound that following formula (I) the means compound as Component units.
[changing 5]
(in formula, R
1, R
2, R
3and R
4be hydrogen atom, alkyl or aromatic group independently respectively, n means positive integer, but R
1, R
2and R
4when different, being hydrogen atom, is aromatic group when different, n R
3can be identical, also can be different.)
It should be noted that, above-mentioned Component units polycondensation forms the compound of random structure with Si-O-Si skeleton, trapezoidal configuration, cage type structure etc.
R in formula (I)
1, R
2, R
3and R
4mean independently respectively hydrogen atom, alkyl or aromatic group, but R
1, R
2and R
4when different, being hydrogen atom, is aromatic group when different, n R
3can be identical, also can be different.That is, R
1, R
2and R
4in at least 1 be alkyl.
R in formula (I)
1, R
2, R
3and R
4the carbonatoms of alkyl from the viewpoint of the reactivity at microparticle surfaces, hydrolysis rate, consider to be preferably 1～4, more preferably 1～2.Particularly, can enumerate methyl, ethyl, propyl group etc.Wherein, be preferably methyl, more preferably OR
1, OR
2, OR
3and OR
4be methoxyl group.It should be noted that, preferably n OR
3it is all also methoxyl group.
N in formula (I) means positive integer, from the deliquescent viewpoint to solvent, considers, is preferably 1～3 integer.
The poly methyl silsesquioxane derivative meaned as above-mentioned formula (I), can enumerate the random structure with Si-O-Si skeleton compound (random), have trapezoidal configuration compound (trapezoidal type), there are the compound (cage modle) of cage type structure, the compound that this cage modle partly ftractures (part ftracture cage modle) etc., they can use separately or combine two or more and used.
Wherein, preferred R
1, R
2, R
3(n R
3all) and R
4be the partial hydrolysis condenses of the poly methyl silsesquioxane derivative of methyl.It should be noted that, in this manual, the partial hydrolysis condenses refers to the material that the mixture hydrolytie polycondensation of the poly methyl silsesquioxane derivative with various structures forms, and composition is not particularly limited.
The preferred commercially available product of the poly methyl silsesquioxane derivative meaned as formula (I), can enumerate " X-40-9225 ", " X-40-9246 ", " KR500 ", " KC89 " of chemical company of SHIN-ETSU HANTOTAI etc., they can use separately or combine two or more and used.
The molecular weight of the poly methyl silsesquioxane derivative in the present invention is preferably 200～5000, and more preferably 200～3000, more preferably 400～3000.It should be noted that, while using two or more poly methyl silsesquioxane derivative, preferably the molecular weight of each poly methyl silsesquioxane derivative is in above-mentioned scope, also comprise the above-mentioned extraneous material of a part, as the molecular weight of poly methyl silsesquioxane derivative integral body, as long as weight average molecular weight is included in above-mentioned scope.In this specification sheets, the molecular weight of organosilicon derivates is measured by gel filtration chromatography (GPC).
The content of alkoxyl group considers to be preferably 10～50 % by weight, more preferably 20～48 % by weight, 24～46 % by weight more preferably 1 molecule poly methyl silsesquioxane derivative from reactive viewpoint.In this specification sheets, the content of the alkoxyl group in 1 molecule poly methyl silsesquioxane derivative can be measured by the method for putting down in writing in aftermentioned embodiment.
The silicone resin of mode 1 is preferably 50～99 % by weight, more preferably 60～95 % by weight, 70～90 % by weight more preferably with in composition, content that have a poly methyl silsesquioxane derivative of alkoxysilyl in molecular end.
The silicone resin of mode 2 is preferably 60～99 % by weight, more preferably 70～95 % by weight, 80～90 % by weight more preferably with in composition, content that have a poly methyl silsesquioxane derivative of alkoxysilyl in molecular end.
In the present invention, the silicone resin of mode 1 is considered from the viewpoint of giving flexibility with composition, as organosilicon derivates, except above-mentioned poly methyl silsesquioxane derivative, also contain the disilane alcohol derivate (following also referred to as the disilane alcohol derivate) that there is silanol group at two ends of molecule.This disilane alcohol derivate by with above-mentioned poly methyl silsesquioxane derivative generation polycondensation, can further form the organosilicon unit that flexibility is high.
As in mode 1, disilane alcohol derivate there is silanol group at two ends of molecule, for example can enumerate the compound that following formula (III) means:
[changing 6]
(in formula, R
5, R
6and R
7be the univalent saturated hydrocarbon radical of non-substituted or replacement or the alkenyl that carbonatoms is 2～10 independently respectively, a means the integer more than 1, but a R
6can be identical, also can be different, a R
7for can be identical, also can be different.)。
R in formula (III)
5, R
6and R
7mean independently respectively the univalent saturated hydrocarbon radical of non-substituted or replacement or the alkenyl that carbonatoms is 2～10, can enumerate the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl particularly; The aryl such as phenyl, tolyl, xylyl, naphthyl, xenyl; The cycloalkyl such as cyclopentyl, cyclohexyl, suberyl; The aralkyl such as benzyl, phenylethyl, phenyl propyl, methyl-benzyl; And an above hydrogen atom of their univalent saturated hydrocarbon radical is by group, for example chloromethyl, 2-bromotrifluoromethane, the 3-chloropropyl, 3 of the replacements such as halogen atom, the cyano group such as fluorine atom, chlorine atom, bromine atoms, 3,3-trifluoro propyl, chloro-phenyl-, fluorophenyl, cyano ethyl, 3,3,4,4,5,5,6,6,6-, nine fluorine hexyls; The alkenyl that the carbonatomss such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, pentenyl, hexenyl, cyclohexenyl are 2～10.Wherein, preferable methyl, phenyl, vinyl or hexenyl.
A in formula (III) means the integer more than 1, but considers from the viewpoint of flexibility and intermiscibility, and a is preferably 1～50, more preferably 1～40 integer.
The disilane alcohol derivate meaned as above-mentioned formula (III), " DMS-S12 ", " DMS-S14 ", " DMS-S151 " of " X-21-3153 ", " X-21-5841 ", " KF9701 ", the Gelest company of chemical company of SHIN-ETSU HANTOTAI etc. are arranged, and they can use separately or combine two or more and used.Wherein, preferred " X-21-3153 ", " X-21-5841 ", " DMS-S12 ", " DMS-S14 ".
The molecular weight of the disilane alcohol derivate that formula (III) means is preferably 200～2000, and more preferably 200～1000.It should be noted that, while using two or more disilane alcohol derivate, preferably the molecular weight of each disilane alcohol derivate is in above-mentioned scope, but also can comprise a part at above-mentioned extraneous material, as the molecular weight of disilane alcohol derivate integral body, as long as weight average molecular weight is included in above-mentioned scope.
Functional group's equivalent of the silanol group of the disilane alcohol derivate that formula (III) means is considered to be preferably 100～1000, more preferably 100～800, more preferably 100～500 from the viewpoint of the affinity with metal oxide microparticle.In this manual, functional group's equivalent of silanol group can pass through
1h-NMR measures.
Be preferably 1～25 % by weight, more preferably 3～20 % by weight, 5～20 % by weight more preferably at the silicone resin of mode 1 with in composition, content that there is the disilane alcohol derivate of silanol group at two ends of molecule.
In addition, in the present invention, the silicone resin of mode 2 is considered from the viewpoint that shows viscosity (tackiness) under heating with composition, is contained the 1 functional silanes derivative (following also referred to as 1 functional silanes derivative) that formula (II) means.
[changing 7]
(in formula, X means alkoxyl group or halogen atom.)
X in formula (II) means alkoxyl group or halogen atom, and the carbonatoms of the alkyl in alkoxyl group is considered to be preferably 1～4, more preferably 1～2 from reactive viewpoint.As the concrete example of alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-etc., as the concrete example of halogen atom, can enumerate fluorine, chlorine, bromine etc.Wherein, from reactive viewpoint, consider, be preferably chlorine.
The 1 functional silanes derivative meaned as above-mentioned formula (II), can enumerate methoxytrimethylsilane, chlorine trimethyl silane, ethoxytrimethylsilane etc., and they can use separately or combine two or more and used.
The preferred commercially available product of the 1 functional silanes derivative meaned as formula (II), can enumerate " LS-510 ", " KA31 " of chemical company of SHIN-ETSU HANTOTAI etc., and they can use separately or combine two or more and used.
The molecular weight of the 1 functional silanes derivative that formula (II) means is preferably 100～160, and more preferably 100～140.
The silicone resin of mode 2 is preferably 1～40 % by weight, more preferably 5～30 % by weight, 10～20 % by weight more preferably with content in composition, 1 functional silanes derivative that formula (II) means.
In addition, the viewpoint of the silicone resin of mode 2 intensity when being formed into body by the weight ratio (poly methyl silsesquioxane/1 functional silanes) of in composition, 1 functional silanes derivative that above-mentioned poly methyl silsesquioxane derivative and formula (II) mean is considered to be preferably 60/40～99/1, more preferably 70/30～95/5, more preferably 80/20～90/10.
In the present invention, can contain in the scope of harmless effect of the present invention above-mentioned poly methyl silsesquioxane derivative, disilane alcohol derivate and 1 functional silanes derivative other organosilicon derivates in addition.As other organosilicon derivates, can enumerate known organosilicon derivates.In the total amount of the organosilicon derivates in mode 1 total content of above-mentioned poly methyl silsesquioxane derivative and disilane alcohol derivate be preferably 80 % by weight above, more preferably 90 % by weight, further preferably be essentially 100 % by weight.In the total amount of the organosilicon derivates in mode 2 total content of above-mentioned poly methyl silsesquioxane derivative and 1 functional silanes derivative be preferably 80 % by weight above, more preferably 90 % by weight, further preferably be essentially 100 % by weight.
As in mode 1 and 2, at microparticle surfaces, thering is the metal oxide microparticle of reactive functional groups, can enumerate titanium oxide, zirconium white, barium titanate, zinc oxide, lead titanate, silicon-dioxide, aluminum oxide etc., they can use separately or combine two or more and used.Wherein, from the viewpoint of high refractive index, consider, be preferably selected from least a kind in titanium oxide, zinc oxide, zirconium white, barium titanate and silicon-dioxide.It should be noted that, as titanium oxide, can use any in Titanium Dioxide (Rutile) Top grade, anatase-type titanium oxide.
As the reactive functional groups in metal oxide microparticle, can enumerate hydroxyl, isocyanate group, amino, sulfydryl, carboxyl, epoxy group(ing), ethylene type unsaturated group, halogen group, isocyanurate group etc.
The reactive functional mass contg of the microparticle surfaces of metal oxide microparticle can be obtained by the surface-area of particulate loading, particulate, surface treatment dosage of having reacted etc., but will be that particulate more than 0.1 % by weight of particulate weight is called " metal oxide microparticle that has reactive functional groups at microparticle surfaces " with the reacting weight of surface treatment agent in the present invention., take the content that this reacting weight is reactive functional groups herein, above as long as the content in metal oxide microparticle is 0.1 % by weight, be not particularly limited.It should be noted that, in this manual, the content of the reactive functional groups on metal oxide microparticle surface can be measured by the method for aftermentioned embodiment, and " content of reactive functional groups " refers to " content " and/or " amount " of reactive functional groups.
In addition, the content of the reactive functional groups of the microparticle surfaces of metal oxide microparticle is for example by reducing solution and particulate reaction that methyltrimethoxy silane is dissolved in organic solvent.In addition, by high temperature burning till particulate, can reduce the reactive functional groups amount of microparticle surfaces.
Metal oxide microparticle can be used the particulate of being manufactured by known method; wherein; consider the particulate that preferably at least 1 manufacture method in being selected from hydrothermal synthesis method, sol-gel method, supercritical water thermal synthesis method, coprecipitation method and the homogeneous precipitator method obtains from homogeneity or the micronized viewpoint of size of particles.
The viewpoint of the transparency of the median size of metal oxide microparticle when composition is made to molding considers to be preferably 1～100nm, more preferably 1～70nm, 1～20nm more preferably.In this manual, the median size of metal oxide microparticle can be measured by the particle diameter with the dynamic light scattering determination particle dispersion or with the direct observation of transmission type microscope.
It should be noted that, metal oxide microparticle is considered to use the particulate (also referred to as " metal oxide microparticle dispersion liquid ") of modulating dispersion liquid from the viewpoint of dispersion stabilization.As dispersion medium, can enumerate water, alcohol, ketones solvent, ethanamide solvent etc., preferably make water, methyl alcohol, methyl butyl ketone, N,N-DIMETHYLACETAMIDE.The amount of the metal oxide microparticle in dispersion liquid (solid component concentration) considers to be preferably 10～40 % by weight, more preferably 15～40 % by weight, 20～40 % by weight more preferably from the viewpoint of being reacted at microparticle surfaces efficiently.For above-mentioned metal oxide microparticle dispersion liquid, as titanium oxide use catalyst change into the NEOSUNVEIL of company or QUEEN TITANIC series, many wooden chemistries company Tynoc, as zirconium white use NZD series, the daily output chemical company of ZSL series, Osaka, Sumitomo cement company of the first uncommon element chemistry industrial NanoUse series, use the commercially available products such as alumina sol of daily output chemical company as aluminum oxide.
The content of metal oxide microparticle is preferably 1～80 weight part, more preferably 10～70 weight parts, 20～60 weight parts more preferably with respect to total amount 100 weight parts of poly methyl silsesquioxane derivative and above-mentioned silane derivative.
The silicone resin of mode 1 is preferably 1～80 weight part, more preferably 10～70 weight parts, 20～60 weight parts more preferably with in composition, content metal oxide microparticle with respect to total amount 100 weight parts of poly methyl silsesquioxane derivative and disilane alcohol derivate.
Total amount 100 weight parts of the 1 functional silanes derivative that the silicone resin of mode 2 means with respect to poly methyl silsesquioxane derivative and formula (II) with in composition, content metal oxide microparticle are preferably 1～80 weight part, more preferably 10～70 weight parts, 20～60 weight parts more preferably.
For silicone resin composition of the present invention, mode 1 is except above-mentioned poly methyl silsesquioxane derivative, disilane alcohol derivate and metal oxide microparticle, mode 2, except above-mentioned poly methyl silsesquioxane derivative, 1 functional silanes derivative and metal oxide microparticle, can contain the additives such as protective agent, properties-correcting agent, tensio-active agent, dyestuff, pigment, variable color preventing agent, UV light absorber in the scope of harmless effect of the present invention respectively.
Silicon resin composition of the present invention is by making silicone resin of the present invention obtain with the composition polymerization reaction take place.Particularly, to the silicon resin composition of each mode, enumerate preferable production process and describe.
The silicon resin composition of mode 1 for example can be as modulated: in above-mentioned metal oxide microparticle dispersion liquid, make the resin solution polymkeric substance obtained at 40～80 ℃ of lower polymerization reaction take places and the resin solution that contains the disilane alcohol derivate that contain the poly methyl silsesquioxane derivative modulate at 40～80 ℃ of lower polymerization reaction take places.
As the preferable production process of the silicon resin composition of mode 1, can enumerate comprise the operation (operation (1-A)) that makes poly methyl silsesquioxane derivative and metal oxide microparticle polymerization reaction take place, and, make the method for the operation (operation (1-B)) of the polymkeric substance that obtains in this operation (1-A) and disilane alcohol derivate polymerization reaction take place.
Concrete example as operation (1-A), for example can enumerate following operation: in the metal oxide microparticle dispersion liquid, add methyl alcohol, ethanol, 2-methyl cellosolve, the 2-propyl alcohol, the organic solvents such as tetrahydrofuran (THF) stir in the liquid obtained, drip to mix the poly methyl silsesquioxane derivative is dissolved in to methyl alcohol, ethanol, the 2-propyl alcohol, in the organic solvents such as tetrahydrofuran (THF), make concentration be preferably 20～50 % by weight and modulate the resin solution obtained, make its reaction 1～3 hour under 40～80 ℃, the operation of the crosslinked configuration of formation poly methyl silsesquioxane derivative and metal oxide microparticle etc.The polymkeric substance obtained is for operation (1-B).
Concrete example as operation (1-B), for example can enumerate following operation: in the polymkeric substance obtained in operation (1-A), drip to mix the disilane alcohol derivate to be dissolved in the organic solvents such as methyl alcohol, ethanol, 2-propyl alcohol, tetrahydrofuran (THF) to the resin solution that makes concentration be preferably 20～50 % by weight and modulate, react the operation etc. of 1～3 hour under 40～80 ℃.It should be noted that, the reaction solution obtained can make its concentrated operation etc. except desolventizing under reduced pressure distillation, adjusts concentration and viscosity.
The silicon resin composition of mode 2 for example can be as modulated: the polymkeric substance that the resin solution that contains the poly methyl silsesquioxane derivative in above-mentioned metal oxide microparticle dispersion liquid obtains at 40～80 ℃ of lower polymerization reaction take places and 1 functional silanes derivative are modulated 40～80 ℃ of lower polymerizations.
The preferable production process of the silicon resin composition of mode 2 be included in microparticle surfaces have reactive functional groups metal oxide microparticle and molecular end have the poly methyl silsesquioxane derivative polymerization reaction take place of alkoxysilyl operation (operation (2-A)), and, the method for the polymkeric substance that obtains in making this operation (2-A) and the operation (operation (2-B)) of 1 functional silanes derivative polymerization reaction take place of formula (II) expression.
Concrete example as operation (2-A), for example can enumerate following operation: in the metal oxide microparticle dispersion liquid, add methyl alcohol, ethanol, 2-methyl cellosolve, the 2-propyl alcohol, the organic solvents such as tetrahydrofuran (THF) stir in the liquid obtained to drip to mix the poly methyl silsesquioxane derivative are dissolved in to methyl alcohol, ethanol, the 2-propyl alcohol, the organic solvents such as tetrahydrofuran (THF) make concentration be preferably 20～50 % by weight and the resin solution modulated, under 40～80 ℃, react 1～3 hour, the operation of the crosslinked configuration of formation poly methyl silsesquioxane derivative and metal oxide microparticle etc.The polymkeric substance obtained is for operation (2-B).
Concrete example as operation (2-B), for example can enumerate following operation: in the polymkeric substance obtained in operation (2-A), drip to mix 1 functional silanes derivative to be dissolved in the organic solvents such as methyl alcohol, ethanol, 2-propyl alcohol, tetrahydrofuran (THF) to the resin solution that makes concentration be preferably 20～50 % by weight and modulate, react the operation etc. of 1～3 hour under 40～80 ℃.It should be noted that, the reaction solution obtained can make its concentrated operation etc. except desolventizing for the lower distillation of decompression, adjusts concentration and viscosity.
The silicon resin composition obtained thus can be by either type, be applied to suitable thickness such as the releasing sheet (such as the polyethylene base material) surface having been carried out to lift-off processing is upper by methods such as cast, spin coating, roller coat, can, except dry at the temperature of desolventizing degree, can be shaped as thus sheet.It should be noted that, the temperature that makes the resin solution drying according to the kind of resin or solvent and therefore difference cannot treat different things as the same, is preferably 80～150 ℃.In addition, drying can divide 2 stages to carry out, and now, the temperature that preferably temperature in the 1st stage is 90～120 ℃, the 2nd stages is 130～150 ℃.
The transparency excellence of silicon resin composition of the present invention, therefore light transmission is high, for example, while being configured as the sheet of thickness 10～500 μ m, to the transmissivity of the incident light of wavelength 400～700nm be preferably more than 80%, more preferably more than 85%, more preferably 90～100%.It should be noted that, in this specification sheets, optical transmittance is measured by the method for putting down in writing in aftermentioned embodiment.
In addition, when the specific refractory power of resin combination of the present invention for example is configured as the thick sheet of 10～500 μ m, be preferably 1.42～1.50, more preferably 1.44～150, more preferably 1.45～1.50.
In other modes of the present invention, provide the silicone resin molding that silicon resin composition of the present invention is shaped and obtains.
Manufacturing process can be used method well known in the art.
For example, the silicone resin molding that is shaped and obtains as the silicon resin composition that makes mode 1, be not particularly limited, from bringing into play the viewpoint consideration of the transparency and the characteristic of high refractive index, be preferably selected from high refractive index silicone resin, microlens, for photosemiconductor in sealing material, pressure sensitive adhesives, sealing agent, organosilicon sheet material and flexible base, board at least 1.
In addition, the silicone resin molding that is shaped and obtains as the silicon resin composition that makes mode 2, can enumerate the silicone based pressure-sensitive adhesive sheet material that the silicon resin composition of mode 2 is coated on to drying on base material and is shaped.
Form and the size of the silicone based pressure-sensitive adhesive sheet material of mode 2 are not particularly limited, can be preferably used as substrate the interlaminar bonding agent, require binding agent of thermotolerance, sunproof electric, electronic part material etc.
Embodiment
Put down in writing by the following examples, disclose mode of the present invention.Above-described embodiment is openly the present invention only, without any the meaning limited.
(molecular weight of organosilicon derivates)
Utilize gel filtration chromatography (GPC) to obtain by polystyrene conversion.
(alkoxy group content of organosilicon derivates)
By using internal standard substance
1the weight minimizing value obtained by differential thermogravimetric analysis that quantitatively reaches of H-NMR is calculated.
(the silanol group functional group equivalent of organosilicon derivates)
By using internal standard substance
1h-NMR measures.
(median size of metal oxide microparticle)
In this manual, the median size of metal oxide microparticle refers to the median size of primary particle, the volume medium (D calculated with the particle dispersion of dynamic light scattering determination metal oxide microparticle
50).
(content of the reactive functional groups on metal oxide microparticle surface)
In particle dispersion liquid, as surface treatment agent, add ethyl trimethoxy silane to make its reaction, by centrifugation or pH change, make the microparticle agglutination sedimentation, filtered and recycled, washing, drying, obtain the weight decrement by differential thermogravimetric analysis and calculate content.
(light transmission of silicon resin composition)
Use spectrophotometer (U-4100, HITECH company of Hitachi system), measure the transmission spectrum of the visible region of 400～800nm, calculate the transmissivity at 400nm place.
Embodiment 1-1
Possessing stirrer, in the container of reflux condensation mode machine and nitrogen ingress pipe, put into the zirconic aqueous dispersions (trade(brand)name " NZD-3007 " of median size 7nm as the metal oxide microparticle that there is reactive functional groups at microparticle surfaces, Osaka, Sumitomo cement company system, solid component concentration 40 % by weight, contain hydroxyl as reactive functional groups, more than reactive functional mass contg 1.0 % by weight) 9.0g (being 40 weight parts with respect to organosilicon derivates 100 weight parts), further add methyl alcohol 9.0g, after 2-methyl cellosolve 9.0g, use concentrated hydrochloric acid, the pH that adjusts liquid is 2.5～3.3.Use dropping funnel to drip therein the poly methyl silsesquioxane derivative (R of trade(brand)name " X-40-9225 ", chemical company of SHIN-ETSU HANTOTAI system, formula (I) that is blended in molecular end and there is alkoxysilyl
1, R
2, R
3and R
4for methyl, molecular weight 2000～3000, methoxy content 24 % by weight) 5.0g is dissolved in the liquid that 2-propyl alcohol 5.0g obtains, under 60 ℃, reaction is after 1 hour, and then, use dropping funnel to drip the disilane alcohol derivate (R of trade(brand)name " X-21-3153 ", chemical company of SHIN-ETSU HANTOTAI system, formula (III) that there is silanol group at two ends of molecule
5, R
6and R
7for methyl, molecular weight approximately 300, functional group's equivalent 150) 4.0 be dissolved in the liquid that 2-propyl alcohol 4.0g obtains, under 60 ℃, reaction, after 2 hours, is cooled to room temperature (25 ℃), obtains silicon resin composition.The composition obtained under reduced pressure distill except desolventizing concentrated after, be applied to thickness 100 μ m on the PET base material of having implemented lift-off processing with silicone based stripper, under 100 ℃, heating is heated 1 hour under 1 hour, 150 ℃, is modulated into thus body a (organosilicon sheet material).
In addition, above-mentioned composition, after concentrated solvent, is applied to thickness 100 μ m on the PET base material of having implemented lift-off processing with silicone based stripper, and under 100 ℃, heating is 8 hours, is modulated into thus body b (organosilicon sheet material).
Embodiment 1-2
In embodiment 1-1, replace zirconic aqueous dispersions (NZD-3007) 9.0g, use aqueous dispersions (trade(brand)name " SNOWTEX OX ", daily output chemical company system, solid component concentration 20 % by weight, as reactive functional groups, the contain hydroxyl) 9.0g (being 20 weight parts with respect to organosilicon derivates 100 weight parts) of the silicon oxide of median size 20nm, replace poly methyl silsesquioxane derivative (X-40-9225) 5.0g, use the poly methyl silsesquioxane derivative (R of trade(brand)name " KR500 ", chemical company of SHIN-ETSU HANTOTAI system, formula (I)
1, R
2, R
3and R
4for methyl, molecular weight 1000～2000, methoxy content 28 % by weight) 5.0g, in addition, (molding is a) similarly to implement to obtain silicon resin composition and molding thereof with embodiment 1-1.
Embodiment 1-3
In embodiment 1-1, replace zirconic aqueous dispersions (NZD-3007) 9.0g, use the aluminum oxide of median size 50～60nm aqueous dispersions (trade(brand)name " alumina sol 520 ", daily output chemical company system, solid component concentration 30 % by weight, as reactive functional groups contain hydroxyl, more than reactive functional mass contg 1.0 % by weight) 9.0g (being 30 weight parts with respect to organosilicon derivates 100 weight parts), in addition, (molding a) similarly to implement to obtain silicon resin composition and molding thereof with embodiment 1-1.
Embodiment 1-4
In embodiment 1-1, replace disilane alcohol derivate (X-21-3153) 4.0g, use the disilane alcohol derivate (R of trade(brand)name " X-21-5841 ", chemical company of SHIN-ETSU HANTOTAI system, formula (III)
5, R
6and R
7for methyl, molecular weight approximately 1000, functional group's equivalent 600) 4.0g, in addition, (molding is a) similarly to implement to obtain silicon resin composition and molding thereof with embodiment 1-1.The usage quantity of metal oxide microparticle is 40 weight parts with respect to organosilicon derivates 100 weight parts.
The molding characteristic of the composition obtained by the method research of following test example 1-1～1-2.The results are shown in table 1.It should be noted that, provide in the lump the light transmission (transmissivity %) of composition in result.
(test example 1-1) (spring rate)
Use determination of viscoelasticity device (DMA, SEIKO INSTRUMENTS company system), measure the spring rate under 25 ℃.
(test example 1-2) (flexibility)
The silicon resin composition of thickness 100 μ m is twisted in respectively on the pipe of diameter 1mm～0.1mm.The condition of surface of visual observations silicon resin composition, the index that the pipe diameter while take the skin breakage of composition is flexibility, by higher evaluation of the less flexibility of diameter.
[table 1]
Table 1
As shown in Table 1, the optical transmittance of the composition of embodiment is high, the spring rate of molding is high, has flexibility simultaneously.
Embodiment 2-1
Possessing stirrer, in the container of reflux condensation mode machine and nitrogen ingress pipe, as there is the metal oxide microparticle of reactive functional groups at microparticle surfaces, put into the zirconic aqueous dispersions (trade(brand)name " NZD-3007 " of median size 7nm, Osaka, Sumitomo cement company system, solid component concentration 40 % by weight, contain hydroxyl as reactive functional groups, more than reactive functional mass contg 1.0 % by weight) 10.0g (being 22 weight parts with respect to organosilicon derivates 100 weight parts), and then interpolation methyl alcohol 10.0g, after 2-methyl cellosolve 10.0g, use concentrated hydrochloric acid, the pH that adjusts liquid is 2.5～3.3.Use dropping funnel to drip and will there is in molecular end the poly methyl silsesquioxane derivative (R of trade(brand)name " X-40-9225 ", chemical company of SHIN-ETSU HANTOTAI system, formula (I) of alkoxysilyl therein with 20 minutes
1, R
2, R
3and R
4for methyl, molecular weight 2000～3000, methoxy content 24 % by weight) 16.0g is dissolved in the liquid obtained in 2-propyl alcohol 16.0g, and under 60 ℃, reaction is 1 hour.Then, as 1 functional silanes derivative, drip methoxytrimethylsilane (X of trade(brand)name " LS-510 ", chemical company of SHIN-ETSU HANTOTAI system, formula (II) is methoxyl group, molecular weight 104.2) 2.5g (poly methyl silsesquioxane/1 functional silanes (weight ratio)=86/14), under 60 ℃, reaction is after 2 hours, be cooled to room temperature (25 ℃), obtain silicon resin composition.The composition obtained under reduced pressure after concentrated solvent, is applied to thickness 100 μ m on the PET base material of having implemented lift-off processing with silicone based stripper, and under 100 ℃, heating is 3 minutes, modulates thus silicone based transparent pressure sensitive bonding sheet material.It should be noted that, the bonding sheet material obtained is at room temperature inviscid, is heated to 60 ℃, shows thus viscosity.
Embodiment 2-2
In embodiment 2-1, replace poly methyl silsesquioxane derivative (X-40-9225) 16.0g, use the poly methyl silsesquioxane derivative (R of trade(brand)name " KR500 ", chemical company of SHIN-ETSU HANTOTAI system, formula (I)
1, R
2, R
3and R
4for methyl, molecular weight 1000～2000, methoxy content 28 % by weight) 16.0g, in addition, similarly implement to obtain silicon resin composition and bonding sheet material thereof with embodiment 2-1.It should be noted that, the bonding sheet material obtained is at room temperature inviscid, by heating under 60 ℃, shows viscosity.
Embodiment 2-3
In embodiment 2-1, replace poly methyl silsesquioxane derivative (X-40-9225) 16.0g, use the poly methyl silsesquioxane derivative (R of trade(brand)name " KC89 ", chemical company of SHIN-ETSU HANTOTAI system, formula (I)
1, R
2, R
3and R
4for methyl, molecular weight approximately 400, methoxy content 46 % by weight) 16.0g, in addition, with embodiment 2-1, similarly implement to obtain silicon resin composition and bonding sheet material thereof.It should be noted that, the bonding sheet material obtained is at room temperature inviscid, by heating under 60 ℃, shows viscosity.
Embodiment 2-4
In embodiment 2-1, methoxytrimethylsilane (LS-50) 2.5g instead of 1 functional silanes derivative, use chlorine trimethyl silane (X of trade(brand)name " KA31 ", chemical company of SHIN-ETSU HANTOTAI system, formula (II) is chlorine, molecular weight 108.6) 2.5g, in addition, similarly implement to obtain silicon resin composition and bonding sheet material thereof with embodiment 2-1.It should be noted that, the bonding sheet material obtained at room temperature inviscid, show viscosity by heating under 60 ℃.
Embodiment 2-5
With the same device of embodiment 2-1 in, put into the aqueous dispersions (trade(brand)name " colloid silica O " of silicon oxide, daily output chemical company system, solid component concentration 20 % by weight, contain hydroxyl as reactive functional groups) 25.8g (being 22 weight parts with respect to organosilicon derivates 100 weight parts), and then interpolation methyl alcohol 20.0g, after 2-methyl cellosolve 20.0g, use dropping funnel to drip therein poly methyl silsesquioxane derivative (KR500) 20.0g is dissolved in to the liquid obtained in 2-propyl alcohol 24.0g, under 60 ℃, reaction is after 1 hour, and then use dropping funnel to drip methoxytrimethylsilane (LS-510) 3.0g (poly methyl silsesquioxane/1 functional silanes (weight ratio)=87/13), under 60 ℃, reaction is after 2 hours, be cooled to room temperature (25 ℃), obtain silicon resin composition.The composition obtained and embodiment 2-1 similarly implement to obtain the sheet material that bonds.It should be noted that, the bonding sheet material obtained at room temperature inviscid, show viscosity by heating under 60 ℃.
Embodiment 2-6
With the same device of embodiment 2-1 in, put into the aqueous dispersions (trade(brand)name " alumina sol 520 " of aluminum oxide, daily output chemical company system, solid component concentration 20 % by weight, contain hydroxyl as reactive functional groups) 25.0g (being 22 weight parts with respect to organosilicon derivates 100 weight parts), and then interpolation methyl alcohol 20.0g, after 2-methyl cellosolve 20.0g, use dropping funnel to drip therein poly methyl silsesquioxane derivative (X-40-9225) 20.0g is dissolved in to the liquid obtained in 2-propyl alcohol 24.0g, under 60 ℃, reaction is after 1 hour, and then use dropping funnel to drip methoxytrimethylsilane (LS-510) 2.5g (poly methyl silsesquioxane/1 functional silanes (weight ratio)=89/11), under 60 ℃, reaction is after 2 hours, be cooled to room temperature (25 ℃), obtain organosilicon resin composition.The composition obtained and embodiment 2-1 similarly implement to obtain the sheet material that bonds.It should be noted that, the bonding sheet material obtained at room temperature inviscid, show viscosity by heating under 60 ℃.
Embodiment 2-7
In embodiment 2-1, replace zirconic aqueous dispersions (NZD-3007) 10.0g, use 15.0g (being 32 weight parts with respect to organosilicon derivates 100 weight parts), in addition, with embodiment 2-1, similarly implement to obtain silicon resin composition and bonding sheet material thereof.It should be noted that, the bonding sheet material obtained at room temperature inviscid, show viscosity by heating under 60 ℃.
Embodiment 2-8
In embodiment 2-1, replace poly methyl silsesquioxane derivative (X-40-9225) 16.0g, use poly methyl silsesquioxane derivative (the partial hydrolysis condenses of trade(brand)name " X-40-9246 ", chemical company of SHIN-ETSU HANTOTAI system, 2 functionality organoalkoxysilanes and 3 functionality organoalkoxysilanes, molecular weight 3000～5000, methoxy content 12 % by weight) 16.0g, in addition, similarly implement to obtain silicon resin composition and bonding sheet material thereof with embodiment 2-1.It should be noted that, the bonding sheet material obtained at room temperature inviscid, show viscosity by heating under 60 ℃.
Comparative example 2-1
In embodiment 2-1, do not use 1 functional silanes derivative, in addition, with embodiment 2-1, similarly implement to obtain the silicon resin composition of comparative example 2-1 and the sheet material that bonds thereof.The usage quantity of metal oxide microparticle is 25 weight parts with respect to organosilicon derivates 100 weight parts.It should be noted that, the bonding sheet material obtained has at room temperature had viscosity, by being heated to 60 ℃ of viscosity, strengthens.
Comparative example 2-2
In embodiment 2-1, methoxytrimethylsilane (LS-510) 2.5g instead of 1 functional silanes derivative, the dimethoxy dimethylsilane chlorine trimethyl silane that use is 2 functional silanes derivatives (trade(brand)name " KBM22 ", chemical company of SHIN-ETSU HANTOTAI system) 2.5g, in addition, similarly implement to obtain silicon resin composition and the bonding sheet material thereof of comparative example 2-2 with embodiment 2-1.It should be noted that, the bonding sheet material obtained has at room temperature had viscosity, by being heated to 60 ℃ of viscosity, strengthens.
The characteristic of the bonding sheet material obtained by the method research of following test example 2-1.The results are shown in table 2.The light transmission (transmissivity %) of composition is shown in result in addition, in the lump.It should be noted that, to reference example 2-1: commercially available tackiness agent (trade(brand)name " SD4560 ", Dong Li Dow Corning Corporation system), reference example 2-2: binding agent (trade(brand)name " SE9185 ", Dong Li Dow Corning Corporation system) is studied characteristic similarly.
(test example 2-1) (stretching slip resistance)
At first, using the bonding sheet material (2cm * 2cm) of embodiment and comparative example respectively by laminater 100 ℃ of lower thermo-compressed on the SUS as by adherend (BA plate), and then another aluminum oxide substrate is pressed from bonding sheet material upper strata, by laminater after 100 ℃ of lower thermo-compressed, under 150 ℃, process 1 hour, carry out the thermofixation reaction, modulation stretching determination of shear strength sample.
Then, use universal tensile testing machine (autograph, company of Shimadzu Seisakusho Ltd. system), measured with the area of attachment of 2cm * 2cm, the draw speed of 50mm/min.
[table 2]
Table 2
| Transmissivity (%) | Stretching slip resistance (N/mm 2) | Viscosity under room temperature (25 ℃) | |
| Embodiment 2-1 | 98 | 106 | Nothing |
| Embodiment 2-2 | 96 | 108 | Nothing |
| Embodiment 2-3 | 96 | 90 | Nothing |
| Embodiment 2-4 | 96 | 107 | Nothing |
| Embodiment 2-5 | 94 | 103 | Nothing |
| Embodiment 2-6 | 84 | 101 | Nothing |
| Embodiment 2-7 | 92 | 68 | Nothing |
| Embodiment 2-8 | 96 | 105 | Nothing |
| Comparative example 2-1 | 96 | 116 | Have |
| Comparative example 2-2 | 94 | 92 | Have |
| Reference example 2-1 | --- | 52 | Have |
| Reference example 2-2 | --- | 145 | Have |
As shown in Table 2, the optical transmittance of the composition of embodiment is high, and the stretching slip resistance of the bonding sheet material of molding is also high, and at room temperature there is no viscosity, so the operability excellence, by heating, shows viscosity, the cohesiveness excellence.In addition, even the composition of embodiment is all placed 500 hours under 200 ℃, transmissivity does not almost change yet, and has excellent thermotolerance.
Silicon resin composition of the present invention is suitable as the material of the semiconductor element of sealing such as backlight, teleseme, outdoor large indicating meter or the billboard etc. of liquid crystal panel.
The obvious existence of the invention described above has the scheme of identity in a large number.Only otherwise break away from intention and the scope of invention, apparent whole change includes in the technical scope of claims above-mentioned diversity for a person skilled in the art.
Claims (10)
1. a silicone resin composition, be to contain in molecular end there is the poly methyl silsesquioxane derivative of alkoxysilyl and there is at microparticle surfaces the silicone resin composition that the metal oxide microparticle of reactive functional groups forms, also contain the disilane alcohol derivate that there is silanol group at two ends of molecule.
2. silicone resin composition as claimed in claim 1, wherein, the median size of metal oxide microparticle is 1～100nm.
3. silicone resin composition as claimed in claim 1, wherein, metal oxide microparticle is dispersed in water, alcohol or their mixture.
4. silicone resin composition as claimed in claim 1, wherein, the content of alkoxyl group is 10～50 % by weight in 1 molecule poly methyl silsesquioxane derivative.
5. silicone resin composition as claimed in claim 1, wherein, functional group's equivalent of silanol group is 100～1000.
6. a silicon resin composition, be after microparticle surfaces has the metal oxide microparticle of reactive functional groups and has the poly methyl silsesquioxane derivative polymerization reaction take place of alkoxysilyl in molecular end, make the polymkeric substance that obtains further and there is the disilane alcohol derivate polymerization reaction take place of silanol group and obtain at two ends of molecule.
7. silicon resin composition as claimed in claim 6, wherein, have in the dispersion liquid in water, alcohol or their mixture of the metal oxide microparticle of reactive functional groups and carry out polyreaction at microparticle surfaces.
8. the manufacture method of silicon resin composition claimed in claim 6, comprise following operation: in molecular end, have the poly methyl silsesquioxane derivative of alkoxysilyl and have the operation of the metal oxide microparticle polymerization reaction take place of reactive functional groups at microparticle surfaces; And make the polymkeric substance obtained in this operation and there is the operation of the disilane alcohol derivate polymerization reaction take place of silanol group at two ends of molecule.
9. a silicone resin molding, it makes silicon resin composition claimed in claim 6 be shaped and form.
10. silicone resin molding as claimed in claim 9, wherein, molding be selected from high refractive index silicone resin, microlens, for photosemiconductor in sealing material, pressure sensitive adhesives, sealing agent, organosilicon sheet material, flexible base, board and silicone based transparent pressure sensitive bonding sheet material at least a kind.
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| JP2008-328412 | 2008-12-24 | ||
| JP2008328412A JP4772858B2 (en) | 2008-12-24 | 2008-12-24 | Silicone resin composition |
| JP2008-328411 | 2008-12-24 | ||
| JP2008328411A JP4850893B2 (en) | 2008-12-24 | 2008-12-24 | Composition for silicone resin |
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2009
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- 2009-12-23 EP EP09015953A patent/EP2202275A1/en not_active Withdrawn
- 2009-12-23 CN CN2009102619227A patent/CN101792529B/en not_active Expired - Fee Related
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| US20100160577A1 (en) | 2010-06-24 |
| EP2202275A1 (en) | 2010-06-30 |
| US8222352B2 (en) | 2012-07-17 |
| CN101792529A (en) | 2010-08-04 |
| KR101569533B1 (en) | 2015-11-16 |
| KR20100075404A (en) | 2010-07-02 |
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